US20030218165A1 - Organic semiconductor device and method - Google Patents

Organic semiconductor device and method Download PDF

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US20030218165A1
US20030218165A1 US10/154,013 US15401302A US2003218165A1 US 20030218165 A1 US20030218165 A1 US 20030218165A1 US 15401302 A US15401302 A US 15401302A US 2003218165 A1 US2003218165 A1 US 2003218165A1
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thin
organic semiconductor
dielectric
semiconductor device
providing
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US6891190B2 (en
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Ke Lian
Robert Croswell
Aroon Tungare
Manes Eliacin
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Motorola Solutions Inc
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Motorola Inc
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Assigned to MOTOROLA, INC. reassignment MOTOROLA, INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: LIAN, KE KERYN, TUNGARE, AROON, CROSWELL, ROBERT T., ELIACIN, MANES
Priority to AU2003251297A priority patent/AU2003251297A1/en
Priority to PCT/US2003/015089 priority patent/WO2003100827A2/en
Priority to TW092114018A priority patent/TWI251358B/en
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    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having a potential-jump barrier or a surface barrier
    • H10K10/40Organic transistors
    • H10K10/46Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H10K10/462Insulated gate field-effect transistors [IGFETs]
    • H10K10/468Insulated gate field-effect transistors [IGFETs] characterised by the gate dielectrics
    • H10K10/478Insulated gate field-effect transistors [IGFETs] characterised by the gate dielectrics the gate dielectric comprising a layer of composite material comprising interpenetrating or embedded materials, e.g. TiO2 particles in a polymer matrix
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00Printed circuits
    • H05K1/18Printed circuits structurally associated with non-printed electric components
    • H05K1/182Printed circuits structurally associated with non-printed electric components associated with components mounted in the printed circuit board, e.g. insert mounted components [IMC]
    • H05K1/185Components encapsulated in the insulating substrate of the printed circuit or incorporated in internal layers of a multilayer circuit
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K19/00Integrated devices, or assemblies of multiple devices, comprising at least one organic element specially adapted for rectifying, amplifying, oscillating or switching, covered by group H10K10/00
    • H10K19/901Assemblies of multiple devices comprising at least one organic element specially adapted for rectifying, amplifying, oscillating or switching
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104Forming layers
    • H01L21/02107Forming insulating materials on a substrate
    • H01L21/02109Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02172Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides
    • H01L21/02197Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides the material having a perovskite structure, e.g. BaTiO3
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/314Inorganic layers
    • H01L21/316Inorganic layers composed of oxides or glassy oxides or oxide based glass
    • H01L21/31691Inorganic layers composed of oxides or glassy oxides or oxide based glass with perovskite structure
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001Technical content checked by a classifier
    • H01L2924/0002Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/095Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00 with a principal constituent of the material being a combination of two or more materials provided in the groups H01L2924/013 - H01L2924/0715
    • H01L2924/097Glass-ceramics, e.g. devitrified glass
    • H01L2924/09701Low temperature co-fired ceramic [LTCC]
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having a potential-jump barrier or a surface barrier
    • H10K10/40Organic transistors
    • H10K10/46Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H10K10/462Insulated gate field-effect transistors [IGFETs]
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K19/00Integrated devices, or assemblies of multiple devices, comprising at least one organic element specially adapted for rectifying, amplifying, oscillating or switching, covered by group H10K10/00

Definitions

  • This invention relates generally to semiconductors and more particularly to organic semiconductor materials.
  • Organic semiconductors have been proposed as an alternative to standard semiconductor paradigms.
  • Organic semiconductors hold the potential for serial or continuous processing and/or otherwise relatively low cost manufacturing requirements.
  • One particularly important goal is to discover materials and methods that would facilitate complimentary exploitation of organic semiconductors using standard printed wiring board materials and methods.
  • FIG. 1 illustrates a first embodiment configured in accordance with the invention
  • FIG. 2 illustrates a second embodiment configured in accordance with the invention
  • FIG. 3 illustrates a third embodiment configured in accordance with the invention
  • FIG. 4 illustrates a fourth embodiment configured in accordance with the invention
  • FIGS. 5 through 11 illustrate a series of steps pursuant to a variety of embodiments in accordance with the invention
  • FIG. 12 illustrates an intermediary step pursuant to another embodiment in accordance with the invention
  • FIGS. 13 and 14 illustrate two steps pursuant to yet another embodiment configured in accordance with the invention.
  • FIG. 15 illustrates yet another embodiment configured in accordance with the invention.
  • an organic semiconductor device is encapsulated within a printed wiring board.
  • a plurality of such devices can be so encapsulated and/or passive components can be similarly embedded therewith.
  • conductive vias can be used to provide an electrical interface to such devices.
  • printed wiring board fabrication techniques are usefully leveraged to form an organic semiconductor device. As to the latter, use of certain ceramic-filled polymer materials or thin-film perovskite materials as a dielectric for the organic semiconductor device serves well.
  • a printed wiring board 10 can be comprised of a variety of materials, including flexible and substantially rigid materials.
  • the board 10 itself should be an insulator such as a glass reinforced composite as is commonly used as a printed wiring board laminate (for example, FR-4 material).
  • Various plastics, including thin flexible sheets such as polyimide generally work well for these purposes.
  • other materials can work as well, including treated cloth and paper.
  • the board 10 can be of various sizes as commensurate with the desired size of the final result.
  • the resultant board 10 will comprise a laminated structure that is formed of numerous thinner layers.
  • an organic semiconductor device 11 is embedded within the board 10 .
  • the device 111 is a FET (field effect transistor) comprised of a gate electrode 12 , a source electrode 14 , and a drain electrode 15 and having a dielectric layer 13 disposed between the gate electrode 12 on the one hand and the source and drain electrodes 14 and 15 on the other hand.
  • An organic semiconductor material 16 lies between the source electrode 14 and drain electrode 15 .
  • printed wiring boards comprise a plurality of laminated layers.
  • a printed wiring board 10 formed of a plurality of individual electrically insulative layers can readily include an organic semiconductor device 11 as generally described above as formed upon a first substrate 20 (such as an FR-4 core).
  • a board 10 can also include one or more embedded mezzanine-layer passive electrical components such as a capacitor 21 .
  • the exemplary capacitor 21 includes two conductive sections 22 and 23 that are separated by a dielectric layer 24 .
  • Such a passive electrical component can be readily electrically coupled to the organic semiconductor device 111 with conductive traces that are formed in accordance with well understood prior art printed wiring board fabrication techniques.
  • Resin 25 can fill in around these embedded components and, if desired, a conductive coating 26 (such as copper) can be disposed over the upper surface to permit ordinary use as a printed wiring board.
  • additional organic semiconductor devices 31 can also be embedded as generally illustrated in FIG. 3 with interconnections again being provided as appropriate to permit formation of one or more desired circuits.
  • Conductive vias can be used to provide such external access.
  • a first conductive via 41 can couple to the gate 12 of the organic semiconductor device 11 and second and third conductive vias 42 and 43 can couple to the source 14 and drain 15 as depicted in FIG. 4. (Formation of such vias is well understood in the art and hence additional description will not be provided here for the sake of brevity.)
  • Forming organic semiconductor devices within a printed wiring board offers a variety of potential advantages.
  • the total required form factor for a given device may be reduced by using this approach (especially when additional devices can be formed or otherwise mounted on the external surface of the board).
  • Special applications are also possible.
  • the embedded circuitry could comprise a display driver. “Blank” boards with such a driver could then be utilized by a given user to support a variety of different circuits placed on the external surface of the board that can make use of such a display without having to design or place the corresponding display driver on those external surfaces.
  • an organic semiconductor device can be embedded in a printed wiring board using standard printed wiring board fabrication techniques.
  • the applicant has also determined, however, that at least for some applications, judicious selection of certain materials permits particular ease of fabrication and performance of the resultant device.
  • Description of various materials and approaches to fabrication will now be provided through various examples (it should also be noted that the described materials and fabrication techniques are suitable for use in forming organic semiconductor devices (and passive electrical components) in general, regardless of whether all or part of the resultant device is embedded within a printed wiring board or resides on a surface thereof).
  • a copper-clad laminate comprising an insulating substrate 20 and a copper layer 51 disposed thereover.
  • the copper layer 51 can range in thickness from 5 to 60 microns (though 10 to 18 microns comprises a good workable range for many purposes).
  • the surface of the copper layer 51 can be treated to at least slightly roughen the surface (such as, for example, by black oxidation or by chemically etching the surface with an anisotropic etch such as MEC Etch, an anisotropic copper etchant produced by MEC Corporation of Japan).
  • a layer 61 of ceramic-filled positive-acting photodielectric polymer such as, for example, Probelec CFP from Vantico A. G. (which has a barium titanate content of about 45 volume percent) is coated over the copper layer 51 (U.S. Pat. No. 6,103,134 provides additional description of ceramic-filled positive-acting photodielectric materials.)
  • This material can be applied using a variety of known printed wiring board fabrication techniques including vertical roller coating, curtain coating, screen printing, and so forth.
  • the CFP thickness can reasonably vary from 5 to 20 microns with 5 to 15 microns comprising a good workable range for many purposes. Portions of this CFP layer 61 will eventually comprise a dielectric portion of an organic semiconductor device. Materials such as Probelec have a dielectric constant of about 21 at 1 MHz and exhibit a loss tangent of 2 to 4%, making the material suitable for this purpose.
  • Various solvents may be used to achieve a good working viscosity of the CFP material during the above coating process. When used, it is useful to drive off at least a portion of such solvents. Drying the CFP material at about 65 to 75 degrees Celsius for approximately 20 minutes will usually suffice for this purpose, leaving a CFP material that remains similar to a B-stage epoxy.
  • a copper layer 71 is laminated on the CFP layer 61 using low lamination temperatures to thereby assure affixment of the copper layer 71 while avoiding altering the photodefinition characteristics of the CFP material itself.
  • a lamination temperature of about 75 degrees Celsius and a pressure of about 180 pounds per square inch for about 20 to 25 minutes should produce acceptable results, especially when slowly ramping the heating and cool down cycles (for example, around 3 degrees Celsius per minute is an acceptable rate of achieving the desired heating temperature and of cooling down from that temperature).
  • the lamination will occur in a vacuum.
  • the copper layer 71 itself can range in thickness from about 5 microns to 18 microns (depending upon the application, however, thinner or thicker layers can be used if desired).
  • source and drain electrodes 14 and 15 are usable to form source and drain electrodes 14 and 15 .
  • the gate distance between these two electrodes constitutes an important parameter and typically needs to be maintained relatively small.
  • gate distances of between about 5 to 75 microns are relatively easily achieved using such known techniques.
  • Standard photomasking techniques are then employed to selectively expose portions of the CFP layer 61 to ultraviolet radiation (note that standard photomasking materials may be useful when masking CFP that underlies the gate section between the source and drain electrodes 14 and 15 ). Portions of the CFP layer 61 that are exposed to such ultraviolet radiation are thereafter rendered more soluble to certain solvents such as Gamma-Butyrolactone (“GBL”).
  • GBL Gamma-Butyrolactone
  • the resultant structure is then exposed to a heat bump of, for example, approximately 110 to 120 degrees Celsius for about 60 to 75 minutes. Such heating tends to render the unexposed portions of the CFP layer 71 less soluble and further renders the ultraviolet exposed portions even more soluble to solvents such as GBL.
  • a solvent such as GBL is used to develop away portions of the CFP layer 71 that were exposed to ultraviolet radiation.
  • the unexposed portion remains and comprises, in this embodiment, the dielectric layer 13 for the organic semiconductor device under construction.
  • the structure will then preferably be baked for about 1 hour at about 150 degrees Celsius to cure the remaining CFP material and hence affix the dielectric materials as well as the laminated copper materials.
  • the exposed copper layer 51 can now be printed and etched using standard fabrication techniques to both form the gate electrode 12 and any other conductive traces and pads as may be desired to support a particular circuit configuration.
  • the copper surface of the source and drain electrodes 14 and 15 are finished with an electroless nickel immersion gold finish.
  • an electroless nickel immersion gold finish aids in ensuring a good Ohmic contact between the source and drain electrodes 14 and 15 and the organic semiconductor material that is later deposited.
  • Other finishes could of course be utilized to achieve this same purpose, including but not limited to palladium, silver, and platinum.
  • organic semiconductor material 16 is deposited at least in the gate between and contacting the source and drain electrodes 14 and 15 via any appropriate process, including screen printing, spin coating, data driven deposition, and so forth.
  • a variety of materials can be used for this purpose, including but not limited to polythiophene (and its various derivatives), pentacene, phthalocyanin, C 60 , and other semiconductor-organic nanocomposites.
  • the resultant FET can demonstrate effective carrier mobility on or below the order of 1 cm 2 /V ⁇ s and current on/off ratios greater than 10 6 .
  • the resultant FET can be readily embedded by depositing subsequent layers of, for example, resin-coated copper material or FR-4 material around and over the FET itself as depicted above. The FET will function properly even if not embedded, of course, thereby rendering the above described techniques useful in both cases.
  • conductive vias can be readily formed to provide electrical connections to embedded portions of such an FET.
  • CFP materials in the above example allows for provision of a good dielectric while simultaneously ensuring that standard printed wiring board techniques are acceptably used and leveraged.
  • Various CFP materials that comprise a photoimagable dielectric-ceramic composite material can be used for these purposes.
  • One particularly useful kind of CFP material to use in this context comprises an epoxy base that is mixed with perovskite particles such as barium titanate (in a preferred embodiment, such particles range in size from approximately 0.2 to 5 microns).
  • This laminated structure 121 includes an intervening layer 61 sandwiched between two copper layers 51 and 71 .
  • the intervening layer 61 comprises, in this embodiment, a thin-film dielectric material such as a thin-film perovskite material.
  • a thin-film dielectric material such as a thin-film perovskite material.
  • dielectric oxides are suitable in this regard, including lead zirconate titanate (PZT), lead lanthanum zirconate titanate (PLZT), lead lanthanide titanate (PLT), lead titanate (PT), lead zirconate (PZ), lead magnesium niobate (PMN), barium titanate (BTO), and barium strontium titanate (BSTO).
  • Dielectric oxides comprising the PLZT approach, particularly compositions comprising a PLZT formula (Pb 1-x La x )(Zr 0.52 Ti 0.48 )O 3 , where x is about 0.15 are particularly attractive.
  • a donor-doped material such as lanthanum to PZT is useful in a preferred embodiment as the lanthanum modifies in a favorable way the electrical properties of the dielectric material.
  • acceptor-doped materials such as nickel, niobium, calcium, and strontium, can also improve electrical performance.
  • a preferred acceptor dopant is calcium, comprising a PCZT formula Pb 1-x Ca x+y (Zr 0.52 Ti 0.48 ) 1-y O 3 , where 0.05 ⁇ x+y ⁇ 0.1.
  • the dielectric oxide used in these embodiments may also contain small quanitites of these elements.
  • the thin-film dielectric material layer 61 can have a thickness of about 0.6 to 1.0 microns. So configured, the resultant structure will have an effective dielectric constant of approximately 200 with a corresponding loss tangent of 0.005 or less. These are acceptable values that, in fact, represent a considerable improvement over current MOSFET capacitance densities.
  • This laminated structure 121 is then itself laminated onto a printed wiring board substrate 20 , thereby yielding a structure that appears as illustrated in FIG. 7. Standard lamination techniques can be utilized to achieve this result.
  • the upper copper layer 71 is then printed and etched to form the source and drain electrodes 14 and 15 .
  • the gate distance between these electrodes can range in size from a few microns to upwards of 50 microns. And again, preferably, a smaller gate size is preferred.
  • etching the upper copper layer 71 will reveal some of the underlying dielectric material, in this case the thin-film ceramic dielectric layer 61 .
  • This thin-film material is now selectively removed, leaving only the portion 13 (see FIG. 9) desired to serve as the intervening dielectric between the gate of the organic semiconductor device being constructed and the source/drain thereof.
  • Such removal can be effected in a variety of ways, including by brushing, pumice scrubbing, laser sciving, and so forth. (A less desirable approach would be to pre-etch the laminated structure 121 prior to laminating that structure 121 to the printed wiring board substrate 20 to form some of the above described elements.)
  • Example 1 The device is now finished using the same techniques as described above in Example 1 to provide an organic semiconductor device as illustrated in FIG. 11. Again, additional insulating layers can be added to partially or fully embed the resultant device and plated vias can be formed as necessary to provide electrical connections to the device when so embedded.
  • Examples 1 and 2 permit fabrication of one or more organic semiconductor devices, which devices are embedded in or otherwise supported on a printed wiring board. As noted earlier, however, it is also possible to form passive electrical components in conjunction with such devices. In this example a capacitor is formed simultaneously with an organic semiconductor device while using CFP material as a dielectric for both devices.
  • Example 1 The process as described above in Example 1 can be followed in a similar manner until the step of printing and etching the top copper layer 71 (see FIG. 7).
  • an electrode 29 for a corresponding capacitor is also defined at this time.
  • Ultraviolet light exposure and heat bumping are again used to define areas within the CFP layer 61 to be retained, and this time, in addition to defining a dielectric layer for the organic semiconductor device a dielectric layer for the capacitor is also similarly defined.
  • the exposed portions of the CFP layer 61 are then removed as before, leaving the dielectric for the organic semiconductor device as before and also a dielectric 28 for the capacitor (as shown in FIG. 14).
  • the second electrode 27 is defined for the capacitor 26 which is now seen to be comprised of two electrodes 27 and 29 having an intervening dielectric 28 .
  • Such a capacitor 26 can now be embedded within subsequent insulating layers as described above, or left as a surface component, as appropriate to the application.
  • conductive traces to allow interconnection of such a capacitor 26 with, for example, the organic semiconductor device 11 , can of course be formed. Or, if these components are embedded within the printed wiring board materials, conductive vias can be formed to provide electrical interconnections to the component electrodes.
  • Example 2 The process set forth above in Example 2 can be similarly modified to also accommodate the formation of one or more passive electrical components.
  • the embodiments and examples described above present the various elements as being stacked in a particular order. Other orientations, however, are possible and acceptable (especially with respect to the device elements themselves).
  • the stacked orientation of the constituent elements can be reversed such the source and drain electrodes 14 and 15 and the intervening organic semiconductor material 16 are disposed proximal to the supporting substrate 20 , with the dielectric layer 13 and the gate electrode 12 being stacked, respectively, thereon.
  • the FET device described in the examples has been used as an illustrative mechanism only. These embodiments are usable with many other organic semiconductor devices and configurations as well.

Abstract

An organic semiconductor device (11) can be embedded within a printed wiring board (10). In various embodiments, the embedded device (11) can be accompanied by other organic semiconductor devices (31) and/or passive electrical components (26). When so embedded, conductive vias (41, 42, 43) can be used to facilitate electrical connection to the embedded device. In various embodiments, specific categories of materials and/or processing steps are used to facilitate the making of organic semiconductors and/or passive electrical components, embedded or otherwise.

Description

    TECHNICAL FIELD
  • This invention relates generally to semiconductors and more particularly to organic semiconductor materials. [0001]
  • BACKGROUND
  • Components and circuits comprised of semiconductor materials are known in the art. Such technology has been highly successful. For some applications, however, traditional semiconductor processing over-performs and represents unneeded form factors and capabilities at a commensurate additional cost. Traditional semiconductor processing also usually requires batch processing to achieve a reasonable cost per part because the fabrication facilities and equipment required are extremely expensive. Also, many semiconductor devices require a lengthy fabrication time and often require numerous chemicals, some of which are highly toxic and require special handling. These aspects of traditional semiconductor fabrication do not well support low data storage and data transmission rate applications and/or other less expensive needs. [0002]
  • Organic semiconductors have been proposed as an alternative to standard semiconductor paradigms. Organic semiconductors hold the potential for serial or continuous processing and/or otherwise relatively low cost manufacturing requirements. One particularly important goal is to discover materials and methods that would facilitate complimentary exploitation of organic semiconductors using standard printed wiring board materials and methods. [0003]
  • BRIEF DESCRIPTION OF THE DRAWINGS
  • The above needs are at least partially met through provision of the organic semiconductor device and method described in the following detailed description, particularly when studied in conjunction with the drawings, wherein: [0004]
  • FIG. 1 illustrates a first embodiment configured in accordance with the invention; [0005]
  • FIG. 2 illustrates a second embodiment configured in accordance with the invention; [0006]
  • FIG. 3 illustrates a third embodiment configured in accordance with the invention; [0007]
  • FIG. 4 illustrates a fourth embodiment configured in accordance with the invention; [0008]
  • FIGS. 5 through 11 illustrate a series of steps pursuant to a variety of embodiments in accordance with the invention; [0009]
  • FIG. 12 illustrates an intermediary step pursuant to another embodiment in accordance with the invention; [0010]
  • FIGS. 13 and 14 illustrate two steps pursuant to yet another embodiment configured in accordance with the invention; and [0011]
  • FIG. 15 illustrates yet another embodiment configured in accordance with the invention.[0012]
  • Skilled artisans will appreciate that elements in the figures are illustrated for simplicity and clarity and have not necessarily been drawn to scale. For example, the dimensions of some of the elements in the figures may be exaggerated relative to other elements to help to improve understanding of various embodiments of the present invention. Also, certain common elements, even though essential to a commercial realization, are often not show for purposes of brevity and preservation of focus. [0013]
  • DETAILED DESCRIPTION
  • Generally speaking, pursuant to some of these various embodiments, an organic semiconductor device is encapsulated within a printed wiring board. If desired, a plurality of such devices can be so encapsulated and/or passive components can be similarly embedded therewith. When so embedded, conductive vias can be used to provide an electrical interface to such devices. In other embodiments, regardless of whether the resultant organic semiconductor device is embedded or not, printed wiring board fabrication techniques are usefully leveraged to form an organic semiconductor device. As to the latter, use of certain ceramic-filled polymer materials or thin-film perovskite materials as a dielectric for the organic semiconductor device serves well. [0014]
  • Referring now to FIG. 1, a first embodiment will be described. A printed [0015] wiring board 10 can be comprised of a variety of materials, including flexible and substantially rigid materials. In general, the board 10 itself should be an insulator such as a glass reinforced composite as is commonly used as a printed wiring board laminate (for example, FR-4 material). Various plastics, including thin flexible sheets such as polyimide, generally work well for these purposes. Depending upon the application, however, other materials can work as well, including treated cloth and paper. The board 10 can be of various sizes as commensurate with the desired size of the final result. Typically, the resultant board 10 will comprise a laminated structure that is formed of numerous thinner layers.
  • Pursuant to this embodiment, an [0016] organic semiconductor device 11 is embedded within the board 10. For purposes of this description, the device 111 is a FET (field effect transistor) comprised of a gate electrode 12, a source electrode 14, and a drain electrode 15 and having a dielectric layer 13 disposed between the gate electrode 12 on the one hand and the source and drain electrodes 14 and 15 on the other hand. An organic semiconductor material 16 lies between the source electrode 14 and drain electrode 15. (Conductive paths to each electrode 12, 14, and 15 would ordinarily be provided to facilitate desired functionality; for purposes of clarity and focus, such paths are not depicted in these figures.)
  • As noted earlier, printed wiring boards comprise a plurality of laminated layers. With reference to FIG. 2, a printed [0017] wiring board 10 formed of a plurality of individual electrically insulative layers can readily include an organic semiconductor device 11 as generally described above as formed upon a first substrate 20 (such as an FR-4 core). Further, such a board 10 can also include one or more embedded mezzanine-layer passive electrical components such as a capacitor 21. In this embodiment, the exemplary capacitor 21 includes two conductive sections 22 and 23 that are separated by a dielectric layer 24. Such a passive electrical component can be readily electrically coupled to the organic semiconductor device 111 with conductive traces that are formed in accordance with well understood prior art printed wiring board fabrication techniques. Resin 25 can fill in around these embedded components and, if desired, a conductive coating 26 (such as copper) can be disposed over the upper surface to permit ordinary use as a printed wiring board.
  • In addition to embedded passive electrical components, of course, additional [0018] organic semiconductor devices 31 can also be embedded as generally illustrated in FIG. 3 with interconnections again being provided as appropriate to permit formation of one or more desired circuits. When embedding organic semiconductor devices within a printed wiring board 10, of course, it will be sometimes desirable to have electrical access to such devices from the exterior of the board 10. Conductive vias can be used to provide such external access. For example, a first conductive via 41 can couple to the gate 12 of the organic semiconductor device 11 and second and third conductive vias 42 and 43 can couple to the source 14 and drain 15 as depicted in FIG. 4. (Formation of such vias is well understood in the art and hence additional description will not be provided here for the sake of brevity.)
  • Forming organic semiconductor devices within a printed wiring board offers a variety of potential advantages. The total required form factor for a given device may be reduced by using this approach (especially when additional devices can be formed or otherwise mounted on the external surface of the board). Special applications are also possible. For example, the embedded circuitry could comprise a display driver. “Blank” boards with such a driver could then be utilized by a given user to support a variety of different circuits placed on the external surface of the board that can make use of such a display without having to design or place the corresponding display driver on those external surfaces. [0019]
  • As noted, an organic semiconductor device can be embedded in a printed wiring board using standard printed wiring board fabrication techniques. The applicant has also determined, however, that at least for some applications, judicious selection of certain materials permits particular ease of fabrication and performance of the resultant device. Description of various materials and approaches to fabrication will now be provided through various examples (it should also be noted that the described materials and fabrication techniques are suitable for use in forming organic semiconductor devices (and passive electrical components) in general, regardless of whether all or part of the resultant device is embedded within a printed wiring board or resides on a surface thereof). [0020]
  • EXAMPLE 1
  • Referring now to FIG. 5, one can begin with a copper-clad laminate comprising an [0021] insulating substrate 20 and a copper layer 51 disposed thereover. The copper layer 51 can range in thickness from 5 to 60 microns (though 10 to 18 microns comprises a good workable range for many purposes). The surface of the copper layer 51 can be treated to at least slightly roughen the surface (such as, for example, by black oxidation or by chemically etching the surface with an anisotropic etch such as MEC Etch, an anisotropic copper etchant produced by MEC Corporation of Japan). Referring now to FIG. 6, a layer 61 of ceramic-filled positive-acting photodielectric polymer (CFP) such as, for example, Probelec CFP from Vantico A. G. (which has a barium titanate content of about 45 volume percent) is coated over the copper layer 51 (U.S. Pat. No. 6,103,134 provides additional description of ceramic-filled positive-acting photodielectric materials.) This material can be applied using a variety of known printed wiring board fabrication techniques including vertical roller coating, curtain coating, screen printing, and so forth. The CFP thickness can reasonably vary from 5 to 20 microns with 5 to 15 microns comprising a good workable range for many purposes. Portions of this CFP layer 61 will eventually comprise a dielectric portion of an organic semiconductor device. Materials such as Probelec have a dielectric constant of about 21 at 1 MHz and exhibit a loss tangent of 2 to 4%, making the material suitable for this purpose.
  • Various solvents may be used to achieve a good working viscosity of the CFP material during the above coating process. When used, it is useful to drive off at least a portion of such solvents. Drying the CFP material at about 65 to 75 degrees Celsius for approximately 20 minutes will usually suffice for this purpose, leaving a CFP material that remains similar to a B-stage epoxy. [0022]
  • Referring now to FIG. 7, a [0023] copper layer 71 is laminated on the CFP layer 61 using low lamination temperatures to thereby assure affixment of the copper layer 71 while avoiding altering the photodefinition characteristics of the CFP material itself. For example, using a lamination temperature of about 75 degrees Celsius and a pressure of about 180 pounds per square inch for about 20 to 25 minutes should produce acceptable results, especially when slowly ramping the heating and cool down cycles (for example, around 3 degrees Celsius per minute is an acceptable rate of achieving the desired heating temperature and of cooling down from that temperature). In a preferred embodiment the lamination will occur in a vacuum. The copper layer 71 itself can range in thickness from about 5 microns to 18 microns (depending upon the application, however, thinner or thicker layers can be used if desired).
  • Referring now to FIG. 8, standard printing and etching techniques are usable to form source and drain [0024] electrodes 14 and 15. The gate distance between these two electrodes constitutes an important parameter and typically needs to be maintained relatively small. Depending in part upon the thickness of the laminated copper layer 71 itself, gate distances of between about 5 to 75 microns are relatively easily achieved using such known techniques.
  • Standard photomasking techniques are then employed to selectively expose portions of the [0025] CFP layer 61 to ultraviolet radiation (note that standard photomasking materials may be useful when masking CFP that underlies the gate section between the source and drain electrodes 14 and 15). Portions of the CFP layer 61 that are exposed to such ultraviolet radiation are thereafter rendered more soluble to certain solvents such as Gamma-Butyrolactone (“GBL”). In a preferred embodiment, the resultant structure is then exposed to a heat bump of, for example, approximately 110 to 120 degrees Celsius for about 60 to 75 minutes. Such heating tends to render the unexposed portions of the CFP layer 71 less soluble and further renders the ultraviolet exposed portions even more soluble to solvents such as GBL.
  • Referring to FIG. 9, a solvent such as GBL is used to develop away portions of the [0026] CFP layer 71 that were exposed to ultraviolet radiation. The unexposed portion remains and comprises, in this embodiment, the dielectric layer 13 for the organic semiconductor device under construction. The structure will then preferably be baked for about 1 hour at about 150 degrees Celsius to cure the remaining CFP material and hence affix the dielectric materials as well as the laminated copper materials. Referring now to FIG. 10, the exposed copper layer 51 can now be printed and etched using standard fabrication techniques to both form the gate electrode 12 and any other conductive traces and pads as may be desired to support a particular circuit configuration.
  • In a preferred embodiment, the copper surface of the source and drain [0027] electrodes 14 and 15 (and any exposed portions of the gate electrode 12) are finished with an electroless nickel immersion gold finish. Such a finish aids in ensuring a good Ohmic contact between the source and drain electrodes 14 and 15 and the organic semiconductor material that is later deposited. Other finishes could of course be utilized to achieve this same purpose, including but not limited to palladium, silver, and platinum.
  • Referring now to FIG. 11, [0028] organic semiconductor material 16 is deposited at least in the gate between and contacting the source and drain electrodes 14 and 15 via any appropriate process, including screen printing, spin coating, data driven deposition, and so forth. A variety of materials can be used for this purpose, including but not limited to polythiophene (and its various derivatives), pentacene, phthalocyanin, C60, and other semiconductor-organic nanocomposites.
  • The resultant FET can demonstrate effective carrier mobility on or below the order of 1 cm[0029] 2/V·s and current on/off ratios greater than 106. If desired, the resultant FET can be readily embedded by depositing subsequent layers of, for example, resin-coated copper material or FR-4 material around and over the FET itself as depicted above. The FET will function properly even if not embedded, of course, thereby rendering the above described techniques useful in both cases. And, again as referenced above, conductive vias can be readily formed to provide electrical connections to embedded portions of such an FET.
  • The use of CFP materials in the above example allows for provision of a good dielectric while simultaneously ensuring that standard printed wiring board techniques are acceptably used and leveraged. Various CFP materials that comprise a photoimagable dielectric-ceramic composite material can be used for these purposes. One particularly useful kind of CFP material to use in this context comprises an epoxy base that is mixed with perovskite particles such as barium titanate (in a preferred embodiment, such particles range in size from approximately 0.2 to 5 microns). [0030]
  • Example 2
  • Another way to achieve a similar result as that described above begins with provision of a [0031] laminated structure 121 as shown in FIG. 12. This laminated structure 121 includes an intervening layer 61 sandwiched between two copper layers 51 and 71. The intervening layer 61 comprises, in this embodiment, a thin-film dielectric material such as a thin-film perovskite material. Many dielectric oxides are suitable in this regard, including lead zirconate titanate (PZT), lead lanthanum zirconate titanate (PLZT), lead lanthanide titanate (PLT), lead titanate (PT), lead zirconate (PZ), lead magnesium niobate (PMN), barium titanate (BTO), and barium strontium titanate (BSTO). Dielectric oxides comprising the PLZT approach, particularly compositions comprising a PLZT formula (Pb1-xLax)(Zr0.52Ti0.48)O3, where x is about 0.15 are particularly attractive. Adding a donor-doped material such as lanthanum to PZT is useful in a preferred embodiment as the lanthanum modifies in a favorable way the electrical properties of the dielectric material. Similarly, addition of small quantities of acceptor-doped materials, such as nickel, niobium, calcium, and strontium, can also improve electrical performance. A preferred acceptor dopant is calcium, comprising a PCZT formula Pb1-xCax+y(Zr0.52Ti0.48)1-yO3, where 0.05<x+y<0.1. Accordingly, the dielectric oxide used in these embodiments may also contain small quanitites of these elements. The thin-film dielectric material layer 61 can have a thickness of about 0.6 to 1.0 microns. So configured, the resultant structure will have an effective dielectric constant of approximately 200 with a corresponding loss tangent of 0.005 or less. These are acceptable values that, in fact, represent a considerable improvement over current MOSFET capacitance densities.
  • This [0032] laminated structure 121 is then itself laminated onto a printed wiring board substrate 20, thereby yielding a structure that appears as illustrated in FIG. 7. Standard lamination techniques can be utilized to achieve this result.
  • As described before with reference to FIG. 8, the [0033] upper copper layer 71 is then printed and etched to form the source and drain electrodes 14 and 15. Again, the gate distance between these electrodes can range in size from a few microns to upwards of 50 microns. And again, preferably, a smaller gate size is preferred.
  • As before, etching the [0034] upper copper layer 71 will reveal some of the underlying dielectric material, in this case the thin-film ceramic dielectric layer 61. This thin-film material is now selectively removed, leaving only the portion 13 (see FIG. 9) desired to serve as the intervening dielectric between the gate of the organic semiconductor device being constructed and the source/drain thereof. Such removal can be effected in a variety of ways, including by brushing, pumice scrubbing, laser sciving, and so forth. (A less desirable approach would be to pre-etch the laminated structure 121 prior to laminating that structure 121 to the printed wiring board substrate 20 to form some of the above described elements.)
  • The device is now finished using the same techniques as described above in Example 1 to provide an organic semiconductor device as illustrated in FIG. 11. Again, additional insulating layers can be added to partially or fully embed the resultant device and plated vias can be formed as necessary to provide electrical connections to the device when so embedded. [0035]
  • Example 3
  • The processes described in Examples 1 and 2 permit fabrication of one or more organic semiconductor devices, which devices are embedded in or otherwise supported on a printed wiring board. As noted earlier, however, it is also possible to form passive electrical components in conjunction with such devices. In this example a capacitor is formed simultaneously with an organic semiconductor device while using CFP material as a dielectric for both devices. [0036]
  • The process as described above in Example 1 can be followed in a similar manner until the step of printing and etching the top copper layer [0037] 71 (see FIG. 7). As shown in FIG. 13, in addition to defining a source and drain electrode 14 and 15 for the organic semiconductor device, an electrode 29 for a corresponding capacitor is also defined at this time. Ultraviolet light exposure and heat bumping are again used to define areas within the CFP layer 61 to be retained, and this time, in addition to defining a dielectric layer for the organic semiconductor device a dielectric layer for the capacitor is also similarly defined. The exposed portions of the CFP layer 61 are then removed as before, leaving the dielectric for the organic semiconductor device as before and also a dielectric 28 for the capacitor (as shown in FIG. 14). Similarly, when the bottom layer of copper 51 is etched, the second electrode 27 is defined for the capacitor 26 which is now seen to be comprised of two electrodes 27 and 29 having an intervening dielectric 28. Such a capacitor 26 can now be embedded within subsequent insulating layers as described above, or left as a surface component, as appropriate to the application.
  • If desired, when etching the [0038] lower copper layer 51, conductive traces to allow interconnection of such a capacitor 26 with, for example, the organic semiconductor device 11, can of course be formed. Or, if these components are embedded within the printed wiring board materials, conductive vias can be formed to provide electrical interconnections to the component electrodes.
  • The process set forth above in Example 2 can be similarly modified to also accommodate the formation of one or more passive electrical components. [0039]
  • The embodiments and examples described above present the various elements as being stacked in a particular order. Other orientations, however, are possible and acceptable (especially with respect to the device elements themselves). For example, with reference to FIG. 15, the stacked orientation of the constituent elements can be reversed such the source and drain [0040] electrodes 14 and 15 and the intervening organic semiconductor material 16 are disposed proximal to the supporting substrate 20, with the dielectric layer 13 and the gate electrode 12 being stacked, respectively, thereon. Furthermore, the FET device described in the examples has been used as an illustrative mechanism only. These embodiments are usable with many other organic semiconductor devices and configurations as well.
  • A wide variety of materials can be used consistently with the above processes and embodiments. Furthermore, a wide range of processing parameters can be varied, including device size and constituent element sizes, to suit a wide variety of application requirements. Those skilled in the art will recognize that a wide variety of modifications, alterations, and combinations can be made with respect to the above described embodiments without departing from the spirit and scope of the invention, and that such modifications, alterations, and combinations are to be viewed as being within the ambit of the inventive concept. [0041]
  • We claim:

Claims (49)

1. A device comprising:
a substrate comprised of electrically insulating material;
an organic semiconductor device embedded within the substrate.
2. The device of claim 1 wherein the substrate is comprised of a glass reinforced composite.
3. The device of claim 1 wherein the substrate is comprised of a plurality of laminated layers of electrically insulating material.
4. The device of claim 3 wherein the organic semiconductor device is disposed on at least one of the plurality of laminated layers of electrically insulating material.
5. The device of claim 1 and further comprising a passive electrical component that is embedded within the substrate.
6. The device of claim 5 wherein the organic semiconductor device and the passive electrical component are electrically coupled to one another.
7. The device of claim 1 wherein the substrate includes at least one via providing electrically conductive access to the organic semiconductor device.
8. The device of claim 1 and further comprising a plurality of organic semiconductor devices embedded within the substrate.
9. The device of claim 1 wherein the organic semiconductor device includes a first electrode and a second electrode, which first and second electrodes are separated at least by a dielectric material.
10. The device of claim 9 wherein the dielectric material comprises ceramic filled polymer material.
11. The device of claim 10 wherein the ceramic filled polymer material has a thickness of approximately 5 to 15 microns.
12. The device of claim 10 wherein the ceramic filled polymer comprises an epoxy base mixed with perovskite particles.
13. The device of claim 12 wherein at least some of the perovskite particles comprise barium titanate.
14. The device of claim 13 wherein at least a substantial number of the perovskite particles range in size from approximately 0.2 to 5 micrometers.
15. The device of claim 12 wherein the ceramic filled polymer comprises a photoimagable dielectric-ceramic composite material.
16. The device of claim 9 wherein the dielectric material comprises a thin-film perovskite material.
17. The device of claim 16 wherein the thin-film perovskite material comprises a lead zirconate titanate-based material.
18. The device of claim 17 wherein the thin-film perovskite material is donor-doped.
19. The device of claim 18 wherein the thin-film perovskite material is donor-doped with lanthanum.
20. The device of claim 17 wherein the thin-film perovskite material is acceptor-doped.
21. The device of claim 20 wherein the thin-film perovskite material is acceptor-doped with calcium.
22. The device of claim 16 wherein the thin-film perovskite material has a thickness of approximately 0.3 to 2.0 micrometers.
23. The device of claim 22 wherein the thin-film perovskite material has a thickness of approximately 0.5 to 1.0 micrometer.
24. The device of claim 9 and further comprising a third electrode, wherein the second and third electrodes are separated from the first electrode by the dielectric.
25. A method comprising:
providing an insulating substrate;
forming at least one organic semiconductor device on the insulating substrate;
forming at least one additional layer of insulating material over the at least one organic semiconductor device and the insulating substrate to provide a laminated printed wiring board having the at least one organic semiconductor device embedded therein.
26. The method of claim 25 and further comprising forming at least one via through the laminated printed wiring board to provide electrical access to the at least one organic semiconductor device embedded therein.
27. The method of claim 25 wherein forming at least one organic semiconductor device includes:
providing at least one conductive electrode;
providing a dielectric overlying at least part of the at least one conductive electrode;
providing at least a second conductive electrode overlying at least part of the dielectric.
28. The method of claim 27, wherein providing a dielectric includes providing a dielectric comprising ceramic filled polymer material.
29. The method of claim 28 wherein providing a dielectric comprising ceramic filled polymer material includes providing a ceramic filled polymer material comprising an epoxy base mixed with perovskite particles.
30. The method of claim 29 wherein providing a ceramic filled polymer material comprising an epoxy base mixed with perovskite particles includes providing a ceramic filled polymer material comprising an epoxy base mixed with perovskite particles wherein at least some of the perovskite particles comprise barium titanate.
31. The method of claim 28 wherein providing a dielectric comprising ceramic filled polymer material includes providing a ceramic filled polymer material that comprises a photoimagable dielectric-ceramic composite material.
32. The method of claim 27 wherein providing a dielectric includes providing a dielectric material comprising a thin-film perovskite material.
33. The device of claim 32 wherein providing a dielectric material comprising a thin-film perovskite material includes providing a lead zirconate titanate-based material.
34. The device of claim 32 wherein providing a dielectric material comprising a thin-film perovskite material includes providing a thin-film perovskite material that is donor-doped.
35. The device of claim 34 wherein providing a thin-film perovskite material that is donor-doped includes providing a thin-film perovskite material that is donor-doped with lanthanum.
36. The device of claim 32 wherein providing a dielectric material comprising a thin-film perovskite material includes providing a thin-film perovskite material wherein the thin-film perovskite material is acceptor-doped.
37. The device of claim 36 wherein providing a thin-film perovskite material wherein the thin-film perovskite material is acceptor-doped includes providing a thin-film perovskite material wherein the thin-film perovskite material is acceptor-doped with calcium.
38. An organic semiconductor device comprising:
a substrate;
a first, second, and third electrode formed at least partially overlying the substrate;
a dielectric material at least partially disposed between the first electrode and the second and third electrodes, wherein the dielectric material comprises one of:
an epoxy base mixed with perovskite particles; and
a thin-film perovskite material; and
an organic semiconductor material at least partially disposed between the second and third electrodes.
39. The organic semiconductor device of claim 38 wherein the dielectric material comprises an epoxy base mixed with perovskite particles and wherein at least some of the perovskite particles are substantially comprised of barium titanate.
40. The organic semiconductor device of claim 39 wherein at least most of the perovskite particles are approximately 0.2 to 5 micrometers in size.
41. The organic semiconductor device of claim 38 wherein the dielectric material comprises an epoxy base mixed with perovskite particles and further wherein the dielectric material is photoimagable.
42. The organic semiconductor device of claim 38 wherein the dielectric material comprises a thin-film perovskite material and further wherein the dielectric material includes a ceramic comprising a lead zirconate titanate-based material.
43. The organic semiconductor device of claim 42 wherein the thin-film perovskite material is donor-doped.
44. The organic semiconductor device of claim 43 wherein the thin-film perovskite material includes donor material comprising lanthanum.
45. The organic semiconductor device of claim 42 wherein the thin-film perovskite material is acceptor-doped.
46. The organic semiconductor device of claim 45 wherein the thin-film perovskite material includes acceptor material comprising calcium.
47. The organic semiconductor device of claim 42 wherein the thin-film perovskite material has a thickness of between about 0.3 and 2.0 micrometers.
48. The organic semiconductor device of claim 47 wherein the thin-film perovskite material has a thickness of between about 0.5 and 1 micrometers.
49. The organic semiconductor device of claim 42 wherein the first, second, and third electrodes, the dielectric material, and the organic semiconductor material are embedded within the substrate.
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